Polymeric alkylene-oxide defoamer material for alkaline aqueous adhesive solutions and the like



POLYMERIC. ALKYLENE-OXIDE DEEOAMER ADHESIVE" FOR ALKALINE AQUEOUS SOLUTIONS AND THE, LIKE John Thomas Stephan, Seatfle, Wash.

No-Drawing. Application August 18, 1958 Serial No..755, 4'32.

19 Claims. (or. 106 -154) This invention relates to an improvement in the control of foam in aqueous alkaline protein. starch, or synthetic resin adhesive solutions, or combinations thereof, and the like.

art of defoaming alkaline adhesive solutions such as are .11. usedin the gluing of wood, the sizing of paper or textiles,

the coating of paper, as agricultural spray stickers, and the like by a polyglycol which is soluble, in ethylene glycol, only' to the extent; of not overparts' of'polyglycol to 90 parts of ethylene glycol, i.e. homopolymers of alkylcue-oxides; having at least three carbon, atoms, or copolymers of at least 2 diiferent alkylene-oxides, or mixtures; of such polymers, wherein the polyglycol has an average molecular weight of at least about 500,

The copolymers of ethylene-oxide with higher alkyleneoxides and propylene-oxide with but'ylene-oxide m-ay'have Particularly this invention is an improvement-in the a more or; less random o'r'hetero distribution of the different oxide groupings alongthe polymer chainv or-t-hey may be block polymers. wherein a substantial portion of the polymer chain consists of one alkylene-oxide interspersed with blocks'of another alkylene-oxide.

Itis well known that alkaline aqueous protein solutions and the like show a marked tendency to roam when agitated or when air or gas is introduced beneath the liquid surface.

such solutions where control of foaming is essentiaL to the success of the operation. The control of "foam is particularly important in the coating of paper, the gluing of "wood or paper,- and the use of protein binders in agricultural sprays. Soybean flour is used inthese applications and others because of its cheapness and special properties. The soybean flour of commerce is one whichhas had the soybean oil extracted from it by solvent extraction. Such extracted soybean ilour is particularly prone to foam and a considerable technology has developed in attempting to economically solve this problem. A particularly bad foamingsituation is created when a toxic material is added toan alkalinqaqueous protein plywood adhesiveto protect said 'adhesi-ve from microbial decomposition.

Toxic materials which give rise to foamingin alkaline aqueous protein adhesives are pentachlorophenol, 2,3,4,6

' tetrachlorophenol, 2,4,5- trichlorophenol, o-phenylphenol, .2 chloro-4 phenylphenol, 4-chloro 2 phenylphenol, 6 ch10.-

There are many examples of; the use of p 7 2,937,104 et n edMey 50 2 in this regard in the specification and the following claims is used to define and include such solutions, dispersions and colloidal suspensions. 7

It is a further object of the present invention to provide improved defoamer materials for solutions of the character indicated, wherein the defoamer materials consist essentially of a polymeric alkelene-oxide, also called polyglycol, soluble in ethylene glycol only to the extent of not over 10 parts of polymer to 90 parts of ethylene glycol, and sufficiently oil soluble to be dissolved in com. mercially employeddefoamer material solvents. In the context of the present invention, by the term substantialvlyinsoluble in ethylene glycol is meant a polymer which is soluble to the extent of not over 10 parts of polymer to 90 parts of ethylene glycol at 70 F.,' and by the term "oilj soluble is meant a polymer which is soluble in a petroleum oil'solvent (Shell TS 28 solvent) to the extent of at least about 1%by weight. Shell TS-28 solvent has; been selected as a typical petroleum oil solvent since it is commonly used in the art as the spreader or vehicle for defoamers. Said TS--28 solvent is characterized by high solvent activity and'identifiable as an aromatic-concentrate containing about 65% aromatics, having a kauri butanol value of 72.5, having a boiling point range of 320 402" F., having a weight per gallon at 60/ 60 F.-

of 7.14 lbs.,' and havingsolvent properties comparable to those of mineral spirits. v

Polyglycols characterizing the present invention are consistent with the above solubility considerations and are homopolymers of alkylene-oxides having at least three carbon atoms, copolymers of alkylene-.oxides' and mix-, tures thereof, wherein the polymer has an average mo lecular Weight of'at least about'SOO. Keeping in mind the indicated average molecular weight requirement, specific homopolymers as above contemplated include polypropylene. glycol and poly-isovbutylene glycol, and speciiiccopolymers include hetero and block polymers of ro-2' phenyl-phenol, o-cresol', p-cresol, mixed isomeric xylenols, andmixtures thereof. All of thesematerials may be used alone or in mixtures-to increase the resistance of a protein adhesive to microbial decomposition. Technical grade materials containing more or less by-product-eimpurities of manufacture. are frequently used. The toxic phenolic materials may beadded either. as. the free phe- --nolic body or as the water soluble salt obtained by treating the phenolic. body with sodium hydroxide, potassiumhy-1 -.-lQida1. suspensions. above indicated. The term- .solutions ethylene-oxide and propylene-oxide and heteroand block polymers of ethylene-oxide and isobuty'lene oxide.

' Apparently the forces which govern solvation and solubility in ethylene glycol are related'to the forces effecting interfacial absorption and defoaming action in alkaline aqueous adhesive solutions'and the like. There the higher the molecular weightthe. more diflicult is the preparation, as apractical matter. All available samples tested of ethylene glycol insoluble polymeric alkyleneoXides prepared, including those up to an average molecular weight of approximately 5000, have been found.

satisfactory. Since, however, the polymers of alkyleneox des progress in consistency from viscous, liquids to plastic solids, it is theoretically. conceivable that some, of

the very high molecular'weights would not have suiiicientsolubility in some commercially used solvent vehicles to satisfy the indicated oil solubility consideration for practical use. Accordingly, to provide a practical upper limit as to average molecular weight of the polymeric alkyleneoxides contemplated by the present invention, an average molecular weight of about 5000 has been assigned. An ethylene glycol insoluble alkylene-oxide. polymer which. is useful in oil solution as. a dust reducing agent for glue powders and as a defoaming agent for aqueous alkaline protein solutions must, as has been indicated, be one which is soluble in a petroleum oil solvent: such as Shell TS-28 solvent to the extent of at least ;l% by :weight. In practice the ethylene glycol insoluble alkylene oxide polymers are extremely effective and small amounts of the order of 0.5 part per 1000 parts of solution. to be defoamed is usually satisfactory. It isjnot necessary that the polymers of alkylene oxides have a highdegree of solubility in oil. Since the polymersof polymer are present in approximately equal quantity have been used. Because they are so highly elfective jthey may be advantageously diluted with inexpensive hydrocarbon solvents such as General Petroleum Solvent No. 10, Shell Solvent TS-28, stove oil, diesel oil, :fuel oil, hexane, carbon tetrachloride, methanol, isopropanol, petroleum, and the like. Usually solvents of low volatility are used; However for some purposes it may .be desirable to use a solvent considerably more volatile than the polyalkylene glycol so that the solvent will evaporate before the ultimate use of the adhesive mixture. I General Petroleum Solvent No. is a predominantly aromatic hydrocarbon solvent having an initial boiling point of 340 F., a final boiling point of 688 F., a kauri butanol value of 76, a flashpoint Penske-Martin closed cup of 210 F., and an A.P.I. gravity of 14.6.

These polymeric defoamer materials may advantageously be dissolved for ease of handling in -a solvent .having a high solubility for the polymeric material to give a defoamer concentrate. Such a defoamer concentrate may be shipped to a consumers plant and then cold ,cut with additional solvent, thus saving freight costs. Such additional solvent may be identical with the original solvent or more likely may be a less expensive solvent .of the hydrocarbon type.

.The defoamer compositions may be used in a number ofdifierent ways; For example, a very convenient method to achieve adequate distribution of the defoamer composition through an adhesive dry mixture is to spray the required amount of defoamer material into the dry adhesive powder, while the adhesive powder is agitated -in a suitable dry mixer, such as a double action helical ribbon mixer. In somewhat similar fashion an oil or volatile solvent solution of defoamer may be sprayed continuously into a soybean flour or an adhesive dry mixture as the flour or mixture moves continuously along a helical conveyor or similar continuous conveyor. Such a method -is particularly Well adapted to adding defoamer in a volatile solvent such as carbon tetrachloride or iso- -.-propanol to soybean flour during the flour milling process where thefiour is conveyed continuously from point to point.

Another convenient method is to make a substantially dry mixture of the soybean flour containing from 10 to -20% of the-defoamer material such that the individual particles of the mixture appear to be thoroughly wetted or coated with the defoamer composition. Such a mixture has a well-oiled appearance and yet does not have so much oil and defoamer present that the oil solution would form a separate liquid phase on standing. Such a mixture may then be dry blended in one or more steps with additional untreated soybean flour or adhesive mixture without lump formation until the desired lower concentration of defoamer material is achieved and the defoamer material is distributed throughout the mass of ad- -hesive material.

In the following examples, except where otherwise indicated, the alkaline proteinaceous adhesive test solution was prepared and the effect of the various anti-foaming compounds or compositions thereon was determined in the following manner. 400 grams of soybean flour was mixed with 1,000 grams water at 70 F., and 18 grams of the indicated defoamer composition were mixed therewith in a mechanical mixer for three minutes. The proprietary product termed Soytex is a finely ground extracted soybean flour, having a protein content of about 44% c and a moisture content of about 8-10%. At the end of this mixing period the resulting mixture was free. from with the revolving roll.

lumps. 40 parts of calcium hydroxide were suspended in 230 parts of water was added to the previous mix and mixed thoroughly with continuous mechanical agitation for three minutes. 44 cc. of a 50% sodium hydroxide (NaOH) solution were added and thoroughly mixed for one minute. grams of sodium silicate were added and mixed one minute. 6 cc. of a liquid mixture containing 75% carbon bisulfite and 25% tetrachloride by weight were added and mixed two minutes. The resulting alkaline proteinaceous adhesive solution was then removed from the mixer and stored, and is essentially in the form used in the manufacture of plywood.

During the experiments to test the relative efficiency of various anti-foaming compositions for foam abatement, a laboratory foam machine closely simulating actual production conditions was utilized. The foam machine employed consisted of a steel roll 8.5 inches in diameter and 6.5 inches long rotated at 144 rpm. in an attached wedge shaped hopper. The total capacity of the hopper was 1200 cc. and approximately 880 cc. of glue solution was charged in the hopper in each instance of experimental test. The gap or slit where the hopper and the roll almostcome in contact was .030 inch wide. The action of the rotating roll in this foam testing machine is-such as to drag glue through the gap or slit and around into the upper part of the hopper, thus causing the glue in the hopper to entrain air as it rolls in contact Thus, the machine accurately tested the glue compositions as to their foaming tendency under production conditions, since a closely similar hopper feeding mechanism and steel roll driven at substantially the same speed are employed in production in the spreading of glue during the manufacture of a laminated product such as plywood. 7

As an accurate measure of the foaming tendency of a given solution, it is to be considered that the specific gravity of the solution provides an accurate measure of such foaming tendency, ormore accurately the degree of air entrainment in the composition. A normal glue solution will usually have a specific gravity at 70 F. of

between 1.00 and 1.15 when freshly mixed. After a given glue solution was subjected to the foaming action for extended periods, the specific gravity was measured and the difference in specific gravity between the initial and foamedglue provided 'an accurate measure of the foaming tendency of the glue. measurements were taken in the following examples after .10, after 20, and after 30 minutes of foam machine Such specific gravity treatment.

In the following examples the proportionate parts of ingredients are somewhat approximate and have been collated to two significant figures from the experimental data.

By way of furnishing preliminary data for later comparison with compositions according to the present in- .vention, a soybean glue solution prepared according to the above procedure without addition of any anti-foaming composition showed a specific gravity after initial mixing of 1.00, and after 10 minutes on the foam machine a specific gravity of 0.49. Extending the time of .the foaming action to 20 minutes further decreased the specific gravity to 0.46, and after 30 minutes treatment the specific gravity was 0.45, in the instance where no anti-foaming composition'was added. In general, it has been found that where the specific gravity after 30 min- -utes of foam test is less than 0.85 the glue is unsatisfactory for application on commercial glue spreader-s and gives rise to excessive foam development.

In order to compare the relative effectiveness of my various defoamer compositions, I have compared them primarily as to their ability to defoam soybean glue. Other glues such as blood glue or casein glue would serve as well for comparative purpose. As will be readily understood. by those skilled in the art, the following examples are merely. illustrative of certain specific embodi- A liquid defoamer composition was made by dissolving together 7.5 grams of a polypropylene glycol prepared by the polymerization of propyleneoxide and having an average molecular weight of 1200, and 36.8 grams sea -.04

of diesel oil. The polypropylene glycol was completely miscible in the diesel oil. The surface tension of water against air when the water is saturated with the defoamer composition was 37.7 dynes/sq. cm. at 70 F. The polypropylene glycol was further characterized as being a viscous oil which is completely miscible in all proporitions in Shell TS-28 solvent and in mineral spirits, in-

soluble in a 6% sodium carbonate solution, and soluble to the extent of only 0.1% by weight in ethylene glycol.

An 880 gram sample of soybean glue, prepared as specified above, was run in the laboratory foam machine and showed a specific gravity after initial mixing of 1.04. After 10 minutes in the foam machine it had a specific gravity of 1.00 and after 30 minutes on the foam machine it had a specific gravity of 0.945.

A similar test was made mixing the adhesivefas hereinbefore described except that just prior to the iaddition of the carbon bisulfide solution a preservative solution containing grams of sodium pentachlorophenate dissolved in 120 grams of water was added to the mixture. When this glue was tested on the foam machine the specific gravity after initial mixing was 1.03 and after 30 minutes on the foam machine it had a specific gravity of 0.90. This demonstrates the effectiveness of this defoamer composition in defoarning -a plywood glue con taining pentachlorophenol preservative.

A similar. test, made in identical fashion as to the addition of sodium 'pentachlorophenate but in the absence of the defoamer composition, showed a specific gravity after mixing of 0.90 and after 30 minutes on the foam machine of 0.60.

Example 11 v A liquid defoamer composition was made by dissolving together 2.5 grams of polypropylene glycol having an average. molecular weight of 3000"and 36.8 grams. of Shell Hexane, Code 8220B, a hydrocarbon having a kauri butanol value of 38.9 and having an initial boiling point of 149 F. and a specificgnavity of 0.709 at 60/60 F.

.defoanier composition was tested exactly as inthe first instance set forth 'in Example I., The specific gravity of'the glue atthe end of the mixing period was 1.035. After 30 minutes on the foam machine the specific gravity of the glue was 0.935.

.Asimil-ar glue was also prepared except that '20 grams of sodium pentachlorophenate dissolved in 120 grams of water were added prior to the addition of the carbon bisulfide solution. The resulting glue had a specific gravity of 1.02 and after 30 minutes on the foam machine it had a specific gravity of 0.85. This should be contrasted I with a specific gravity of 0.60 obtained after 30 minutes The polypropylene glycol was completely miscible in the solvent. The surface tension dfwater against air whenthe water is saturated with the defoamer composition is 37.3 dynes per sq. cm. at 70 F. The polypropylene glycol was further characterized by being completely miscible in all proportions in benzene and in mineral spirits and. only soluble to the extent of 0.5 in ethylene glycol at 70 F. 5 This defoamer composition was tested exactly as in thefirst instance set forth in Example I. Thespecific gravity of the glue at the end of the mixing period was 1.03. After 30 minutes on. the foam machine the specific gravity of the glue was 0.9.6.

Example III s'urface tension of water against air when the-water is atur ed; vi l r e m v mposi o s- 9 ynes p sq. cm at 70-? F. The polymer, was further character- V inedeby being soluble ;to..the extent'Io-f. 110%. by: weight in benzene, only 5% by weight in ethylene glycol, and

miscible-in.allproportionsinwater.

on the foam machine for similar adhesive containing no defoamer, as set forth in Example I. I

Example IV A liquid defoamer composition was made bydissolving together 2.5 grams of an ethylene oxide-butylene oxide random copolymer containing 30% ethylene-oxidefand having anaverage molecular weight of 2000, and 36.8 grams of toluene.

The mixed alkylene-oxide copolymer was completely soluble in the toluene. against air when the water is saturated with the defoamer composition is 32 dynes' per sq., cm. at The polymer was further characterized by being soluble to the extent of 14% by weight-in benzene and 0.1% by' weight in ethylene glycol.

This defoamer composition was tested exactly as in the:

first instance set forth in Example I. The specific gravity" of the glue at theend of the mixing period was 1.04.. 7

After 30 minutes on the foam machine the specific gravity" of the glue was 0.90.

7 Example V A defoamer composition was made by dissolving to-- gether 2.5 grams of an iso-butylene-oxide polymer hav-- inglan average molecular weight of 600, and 36.8 grams.

a of diesel oil. The polymer of iso-butylene-oxide, which.

.Cm. at 70 F. 1 The butylene-oxide polymer was further characterized by being soluble to the extent of 18% by weight in the diesel oil and only 0.05% by weight in ethylene glycol. This defoamer composition was tested exactly as in the first instance set forth in Example I. The specific gravity of the glue at the end of the mixing period was 1.08.. After 30 minutes on the foam machine the specific gravity of the glue was 0.96. This example demonstrates the excellent foam depressing property of an oil solution of a polybutylene glycol. A similargl'ue was also prepared except that 20 grams of sodium tetrachlorophenate dissolved in 120-grams of water were added; prior to the addition of the carbon bisulfide solution. The resulting plywood glue had a specific gravity of 1.05 and after 30 minutes on the foam. machine, had 'a specific gravity of 0.91.

Example V1- In many applications where my defoamer composi tions are, useful the colloidal adhesive solution is spread "by means of a rubber roll glue spreader. The common defoamers such as steam distilled pine oil or tri-butyl phosphate heretofore used are notoriously bad in swelling natural rubber. In the plywood industry, for example, glue spreaders now practically all use polychloroprene rubber totry swelling of the T0118. u Unfortunately polychloroprene'rubber is still swollen 'by- 'defoamer: materials such as pine oil and the like. (af particular'ihterest is thefact that thepolyalkylene glycols-pf'the present" invention do not swell polychloro= and overcome this problemof the The, surface tension of water Example I.

prene rubber and defoamers compounded them heretofore used. This is an important advantage since once a set of rubber covered rolls is swollenthe only remedy is to strip off the swollen rubber and replace with new rubber. This is an expensive operation costing about $300 for a pair of'rolls 10 in diameter and 6 feet long such as are standard in the Douglas fir plywood industry. It is thus seen that important economic advantage is obtained by using my defoamer.

A comparison was made of the swelling of polychloroprene rubber strips cm. long and 0.3 cm. by 0.3 cm. in cross-section after immersion in various liquids for up to 7 days at 70 F. including the polyalkylene glycols of the various examples. The percent elongation of the rubber specimen is reported.

Percent elongation Liquid 1 day imrnersion 7 days immersion In all cases where a polyglycol is dissolved in some solvent and this solution is ttested for its ability to swell polychloroprene rubber,'it has been found that the swelling due to the defoamer composition is to no more than the swelling due to the solvent alone.

Example VII A defoamer composition was made by dissolving together 2.5 grams of polypropylene glycol having an average molecular weight of 750 and soluble to the extent of slightly less than 10% in ethylene glycol, and

36.8 grams of diesel oil. This defoamer composition was tested exactly as in the first instance as set forth in The specific gravity of the glue at the end of the mixing period was 1.03, and after 30 minutes on the foam machine showed a specific gravity of 0.87.

For comparison purposes, a test composition made up of 2.5 grams of a polypropylene glycol having a molecular weight of about 400, and which was soluble in ethylene glycol in all proportions, was dissolved in 36.8 grams of diesel oil and tested in the same manner (18 grams of solution in 400 grams of soybean flour as in Example I), with the following results. The initial specific gravity after mixing was measured as 0.975, and after 30 minutes on the foam machine, as 0.405. This latter comparison composition effectively demonstrates the inoperability of a polypropylene glycol which is soluble in ethylene glycol, insofar as the purposw and characteristics of the present invention are concerned.

Example VIII A defoamer composition was made by dissolving together 2.5 grams of a copolymer of ethylene-oxide and propylene-oxide, in which the ethylene-oxide content was about 10%, which copolymer was insoluble in ethylene glycol, said copolymer being dissolved in 36.8 grams diesel oil. Testing this defoamer composition also exactly as in the first instance set forth in Example I, the initial specific gravity at the end of the mixing period was 1.02, and after 30 minutes on the foam machine'the specific gravity was 0.86.

For comparison purposes, a defoamer composition comparable to the defoamer composition previously presented in this example 'but made from a copolymer of ethylene-oxide and propylene-oxide having an average molecular weight of 400, showed that the polyglycol was soluble in ethylene glycol to the extent of slightly more foamer composition to alkaline adhesive solutions of the than 10% an'd that, while the initial specific gravity after a This example again demonstrates that a copolymer of ethylene-oxide and propylene-oxide, having a sufliciently 'high'molecular weight and having a sufiiciently low solubility in ethylene glycol, has the efficacy characteristic of the present invention as a defoamer in a protein aqueous adhesive, and that if the indicated molecular weight and solubility characteristics are deviated from, then the composition becomes comparatively ineffective as such a defoamer.

Example IX In order to demonstrate the applicability of the deresin type, the following example is presented.

Forasite SW-1920, an aqueous alkaline phenol formaldehyde resin containing about 41% resin solids was selected, as such is commonly used in the manufacture of hardboard. 9 grams of Forasite. was mixed with 291 grams water, giving a 3% resin solution, and 12 ml.

of 4% H SO was added, resulting in the solution having a pH of 8. 30 cc. of such resin solution was P aced in a 100 ml. glass graduate, stoppered, and shaken vigorously by hand for twenty strokes, after which the solution was found to have a volume of ml., signifying the presence of 55 ml. of entrapped air immediately after shaking. To a similar resin solution (30 ml.) there was added one drop cc.) of an oil solution of Polyglycol B-500, a polybutylene glycol of average molecular weight of 500, such solution consisting of 2.5 grams of the polybutylene glycol in 36.8 grams diesel oil. The resin solution, with the defoamer composition added, was shaken as before, and the resulting solution had a volume of 45 ml., signifying the presence of 15 ml. of entrapped air immediately after. shaking. This mode of testing is directly comparable to commercial utilization practices for this type of glue solution because resin adhesives as employed in the hardboard and like fields are highly diluted and normally delivered as a continuous process (presenting a continuous agitation problem), while plywood practice where use of soybean and like proteinaceous adhesives is common is essentially a batch type process where the adhesive often must stand on the applicator rolls for extendedperiods.

Example X To demonstrate the applicability of the present invention to a predominately starch type adhesive, and to also provide a further example of utilization of the defoamer composition of the present invention is a starchy, resincontaining adhesive solution, the following example vis presented. 7

200 grams of wheat flour containing about 68% starch and about 10% protein, was mixed with a total of 1800 grams water, 40 grams of 50% causticsoda solution, and 20 grams of the Forasite resin referred to in Example, IX. The composition mixture was prepared by slurrying the wheat flour in about 1500 grams .water, then slowly adding the caustic soda solution and the balance of the water while stirring over a period of about two minutes,.then adding the Forasite brand resin with stirring for an additional two minutes.- i

The foregoing adhesive composition was. selected because it is a type of adhesive composition that is'a more practical commercial example than'starch alone, and is nevertheless predominately starchy since the amount of resin in the composition approximates seven times. the amount of resin.

Testing this starch-resin adhesive solution, an initial specific gravity after mixing of 0.925 was revealed. After 30 minutes on the foam machine, the specific gravity was 0.485.

Using the starch-resin composition delineated above,

1 distilled pine oil. t s

used in Example IX, the defoamed adhesive solution.

foam machine of 0.860. Etqm e X T d ta th nonp i bi t o P y yle glycols for purposes of the present invention, a test soluflea stem f po y e lyc having a a e a e mq esular wei h Q 66Q Wa dissolved in 36.8 am o es O l Thisr y w s mi ible ethylene glycol in all proportions. This test solution was s ed; eaaqtl s t. tq h nth r ns n E p I .(l8 g of test solution in a soybean adhesive solution n a n rams f o bea fl u t h result that, after an initial specific gravity of 0.99, the adhesive showedaspeciiic gravity of 0.645 on the foam machine.

11 s il t s u icm. ompou ded nd es e s b v b u i in arole -lene glycol ha in an average molecular weight of 3520, an' initial specific gravity of 1.015 was obtained, and a specific gravity of 0.765 after 3.0 minutes on the foam machine was revealed.

demonstrated a specific gravity after 30 minutes on the Thetests example demonstrate that polyethylene, glycols are not utilizable for purposes of the present invention, regardless of their average molecular weight.

g Example; XII I In order to show the non-applicability and comparative ineifectiveness of polyethylen'e jglycol esters, a test solution of 2.5 grams. polyethylene} glycol monostea'ra'te havingan average molecular weight 'of..-400 as. to the polyetl' yleneglyco v P rtion was rnixed with 36i8 grams diesel,

oilfand was. tested'exactlyf in the same way. as. set forth in the first instance inExample I.

This. test adhesive solutionfldisplayed an initial specific gravity after mixing of 1.045, after lO minutes onv the foam machine a specific gravitylof0.85, after 20 minutes onthe foam. machine a'specific gravity of 0.775, and after 3.0. minutes on the foam machine a specific gravity of 0.76 5.

One advantage of my invention is that the solutions blood, peanut flour, starch and. the.lilge,,whereby the surfaces of, individual adhesive material particles are wetted or oiled sufiicientlyjto. greatly reducedusting of o the adhesive materials duringfbulk handling such asoccursiduring bagging dry adhesivesprior tofshipment to the customer and again when used by the customer.

' There is 'a definite improvement in the de-dusting. effect of thealkylene oxide-polymer oil. solutions over oil alone. This is probably due to the ability of the polyglycol to retard thedevelopment of; static electricity charges on the adhesive material particles. Usually from 1 to redu edust ng nd pr vi efc m con o In usingthe above-indicated polymers and copolymers of defoamer based-on adhesive material is adequate to wellas such features and advantages as are inherent "from the: disclosed nature and characteristics of the presscut invention, various other compositions, formulations I and applications Within the scope thereof will occur to those skilled in the art, consistent with the spirit and scope of the invention, as defined by the'fo-llowing claims.

This application'is a continuation-in-part of my copending application Serial-No. 585,965, entitled Polymeric Alkylene-Oxide .Defoamer Materialf; filed May 21,

195.6,now abandoned.

What is claimed is:

1-. A dry, proteinaceous adhesive mix containing m.- 7 over about 51% by Weight of a defoamer material comprising a polyglycol-selected from the group. consisting of homopolymers of alkylene-oxides having at least three carbon atoms, copolymers of alkylene-oxides, and mix- I tures thereof, said polyglycol being, soluble. in ethylene glycol only to-the extent of not over 10 parts ofpolyglyt l to:9,0; parts of ethylene glycol, and being present in an amount-eflective'to render said dry adhesive substantially non-dusting. V 1

2. A dry, proteina ceous adhesive mix containing: not

overabout 5% byweight of a defoamer material consisting essentially of an oil. solution of a polyglycol selected from the. group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, co-

' polymers of alkylene-oxides, and mixtures thereof, said polyglycol beingsoluble in ethylene glycol only to the extent of not over 1.0 parts of polyglycol to 90 parts of ethylene glycol, and being present in an amount effective to render said dry adhesivemix substantially non-dusting.

3., ry, PrQteinaceous adhesive material containing not over about 5%. by Weight of a polyglycol selected from the. group. consisting of homopolyrners of alkyleneoxides having at least three carbon atoms, copolymers of alkylene-oxides, and mixtures thereof, said polyglycol being soluble in ethylene glycol to the extent of not over 10% by weight and having an average molecular weight of at least about 500, said. polyglycol being. present in an ofalkylene' oxideslit will be readily understood that they may be-used singly or in combination "with each jother and/or u t fithfl q atat h e ancest ies-sent:

' Due .to thepolymeric, nature, of my new defoarner compositionsthey are substantially less volatile than come monly used defoamers such as alpha-terpineol or steam in a plywood mill for example.

In view of the foregoing considerations and examples,

amount effective to render said-material substantially nondusting. and said adhesive material therebybeing in a I o a form suitable for admixture in the field with aqueous of. polyalkylene glycols in 011 are easily sprayed intofine 7 ground adhesive materials. such as soybean flour, soluble adhesive solution forming materials, the saidpolyglycol at such time also functioning to inhibit formation of foam in the solution when agitated.

4. Solvent extracted ground soybean material in dry form, containing not over'about 5% by weight of a polyglycol; selected-from the group consisting of homopolymers of alkylene-oxides having atlleast three carbon atoms, copolymers of 'alkylene-oxides, and mixtures thereof, said polyglycol being soluble in'ethylene glycol to the extent; 0t not over 1.0% by weight and having an average molecular weight of at least about 500, said polyglycol being present in an amount effective to render said material substantially non-dusting and said adhesive mate rial thereby being in a form suitable for admixture in the field with aqueous adhesive solution forming materials, the said polyglycol at such time also functioning to inhibit formation of foam in the solution when agitated;

5. Ground soybean material according to claim 3, further containing;- an efiective amount of a polychlorophente s n as a pres r a i e. 6. The process of preparing the solvent extracted ground; soybean material specified in claim '4, wherein the fiidpolyglycol is intimately admixed with the soybean ma r al by pr y 7. The processof preparing the ground soybean mater al. speclfied in claim 4', comprising mixing a sufiicient quantity of the polyglycol with the soybean material to" substantially wetqalljof the. individual soybean material particles in a pre-mix, and continuing additions of soybean material and mixing until the polyglycol is distributed substantially uniformly throughout the mass of the soybean material.

8. A proteinaceous, aqueous adhesive solution containdifferent alkylene-oxides, and mixtures of such polymers,

the said polyglycol having an average molecular weight of at least about 500. t

9. In a proteinaceous, aqueous adhesive solution a de foamer comprising an oil solution of a polyglycol soluble in ethylene glycol only to the extent of not over parts of polyglycol to 90 parts of ethylene glycol, and selected from the group consisting of homopolymers of alkyleneoxides having at least three carbon atoms, alkylene-oxides, and mixtures of such polymers, wherein the polyglycol has an average molecular weight of at least about 500.

10. A proteinaceous, alkaline aqueous adhesive solution having incorporated therewith a defoamer comprising an oil solution of a polyglycol having an average molecular weight of from about 500' to about 5000 and soluble to the extent of not more than 10 parts of polymer to 90 parts of ethylene glycol, the said polyglycol being selected from the group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, copolymers of alkylene-oxides, and mixtures thereof.

11. A proteinaceous, aqueous adhesive solution having incorporated therewith a defoamer material consisting essentially of a polyglycol selected from the group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, copolymers of alkylene-oxides, and mixtures thereof, said polyglycol being soluble in ethylene glycol only to the extent of not over 10 parts of polyglycol to 90 parts of ethylene glycol, and having an average molecular weight of at least about 500.

12. A proteinaceous alkaline aqueous adhesive composition comprising a foam inhibitor consisting essentially of an oil solution of a polyglycol having an average "molecular weight of from about 500 to about-5000 and soluble to the extent of not more than 10 parts of polymer to 90 parts of ethylene glycol, the said polyglycol being selected from the group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, copolymers of alkylene-oxides, and mixtures thereof.

13. A defoamed, proteinaceous aqueous adhesive solution having a defoaming agent consisting essentially of an oil solution of a polyglycol having an average molecular weight of at least about 500 and soluble to the extent of not more than 10 parts of polymer to 90 parts of ethylene glycol, the said polyglycol being selected from the group consisting of homopolymers of propylene glycol and iso-butylene glycol, copolymers of ethylene-oxide and propylene-oxide, copolymers of ethylene-oxide and isobutylene oxide, and mixtures thereof.

14. A defoamed, proteinaceous aqueous adhesive composition of the character indicated, comprising an oil soluble polyglycol soluble in ethylene glycol only to the extent of not over 10 parts of polyglycol to 90 parts of ethylene glycol and having the capability of imparting a surface tension of less than 38 dynes per sq. cm. to a water solution saturated at 70 R, which polyglycol is.

selected from the group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, copolymers of alkylene-oxides, and mixtures thereof, said polyglycol being substantially insoluble in ethylene glycol and having an average molecular weight of at least about 500.

15. A proteinaceous adhesive solution of the character indicated, comprising a defoamer consisting essentially of a solution of a polyglycol in petroleum oil solvent, wherein said polyglycol is soluble in ethylene glycol to the extent of not over 10% by weight, imparts a surface tension of less than 38 dynes per sq. cm. to a water s0 lution saturated with said polyglycol solution at 70 F. and said solution swells Neoprene rubber to an extent of not more than the swelling due to the solvent alone, the said polyglycol being selected from the group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, copolymers of alkylene-oxides, and mixtures thereof, having an average molecular weight of at least about 500. I

16. A proteinaceous adhesive solution containing a foam inhibiting amount of a polyglycol soluble in ethylene glycol only tothe extent of not more than 10% by weight, which polyglycol is selected fom the group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, copolymers ofat least 2 different alkylene-oxides, and mixtures of such polymers, the said polyglycol having an average molecular weight of at least about 500.

17. An aqueous soybean adhesive solution containing a defoamer comprising a polyglycol soluble in ethylene glycol only to the extent of not more than 10% by weight, and is selected from the group consisting of homopolymers of alkylene-oxides having at least three carbon atoms, alkylene-oxides, and mixtures of such polymers, wherein the polyglycol. has an average molecular Weight of at least about 500.

18. A dry adhesive mixhaving as a primary ingredient a potentially adhesive proteinaceous material in particulate form and having dispersed through said material a defoamer composition consisting essentially of apolyglycol dissolved in a substantially water insoluble, substantially non-volatile solvent vehicle, said polyglycol having the property of being soluble in ethylene glycol only to the extent of not over 10% by weight and, being selected from the group consisting of homopolymers of a1- kylene-oxides having at least three carbon atoms, copolymers -of alkylene-oxides, and mixtures thereof, the said defoamer composition being present invsaid mix in an amount effective to render same substantially nondusting and toinhibit foaming thereof when the mix is agitated in aqueous solution.

19. A proteinaceous, alkaline aqueous adhesive composition comprising an aqueous solution of a proteinaceous adhesive material having incorporated therewith, a foam inhibitor consisting essentially of a polyglycol dissolved in a substantially water insoluble, substantially non-volatile solvent vehicle therefor, said polyglycol having the property of being soluble in ethylene glycol only to the extent of not over 10% by weight and being selected from the group consisting vof homopolymers of alkylene-oxides having at least threecarbon atoms, copolymers of alkylene-oxides, and mixtures thereof, the said foam inhibitor being present'in said adhesive composition in an amount effective to inhibit foaming thereof when agitated.

OTHER REFERENCES,

Pluronics, Wyandotte Chemical Corp. (1954), pp. 4and 8. i Y 

4. A SOLVENT EXTRACTED GROUND SOYBEAN MATERIAL IN DRY FORM CONTAINING NOT OVER ABOUT 5% BY WEIGHT OF A POLYGLYCOL SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF ALKYLENE-OXIDES HAVING AT LEAST THREE CARBON ATOMS, COPOLYMERS OF ALKYLENE-OXIDES, AND MIXTURES THEREOF, SAID POLYGLYCOL BEING SOLUBLE IN ETHYLENE GLYCOL TO THE EXTENT OF NOT OVER 10% BY WEIGHT AND HAVING AN AVERAGE MOLECULAR WEIGHT OF AT LEAST ABOUT 500, SAID POLYGLYCOL BEING PRESENT IN AN AMOUNT EFFECTIVE TO RENDER SAID MATERIAL SUBSTANTIALLY NON-DUSTING AND SAID ADHESIVE MATERIAL THEREBY BEING IN A FORM SUITABLE FOR ADMIXTURE IN THE FIELD WITH AQUEOUS ADHESIVE SOLUTION FORMING MATERIALS, THE SAID POLYGLYCOL AT SUCH TIME ALSO FUNCTIONING TO INHIBIT FORMATION OF FOAM IN THE SOLUTION WHEN AGITATED. 